Improved total conductivity of nanometric samaria-doped ceria powders sintered with molten LiNO3 additive

Nanometric 20% molar Sm-doped ceria (SDC20) powders were synthesized by co-precipitation in the presence of N, N, N′, N′ tetramethylethylendiamine (TMEDA). SDC20 powders were sintered using lithium nitrate salt in various concentrations (0.1, 1, 3, and 10 mol% with respect to the SDC20 total moles) as an additive to promote the liquid phase sintering and without additive for comparison. The addition of the Li salt allowed reducing significantly the sintering temperature of SDC. Electrochemical impedance spectroscopy (EIS) measurements were performed to estimate the contribution of grain boundary and bulk to the electrical conductivity in different sintering conditions. Liquid phase sintering allowed to produce dense samples with enhanced ionic conductivity especially at the grain boundary when compared to the samples sintered without additive. The additive liquid phase was evaporated in large part at the high temperatures throughout the sintering process. Residual extra phases were segregated at the grain boundary, generated probably by reaction of the Li salt with impurities, which were removed by a chemical etching.     

TBAC/TBHP体系下6-氨基甲酰基取代的啡啶类化合物的合成

采用2-异氰基联苯与N,N-二甲基甲酰胺(DMF)作为反应原料, 在四丁基氯化铵(TBAC)、 磷酸氢二钾(K₂HPO₄)和叔丁基过氧化氢(TBHP)组成的催化氧化体系作用下, 通过一步构建2个C—C键, 以较高的产率合成了一系列6-氨基甲酰基取代的啡啶类化合物(产率高达86%). 同时利用该方法研究了一系列含有推电子和吸电子取代基的2-异氰基联苯衍生物的普适性, 为具有药物活性的该类分子的合成提供了一种新的方法.     

Cascade reaction for the synthesis of polycyclic aromatic hydrocarbons via transient directing group strategy

A Pd(II)-catalyzed cascade synthesis of diverse polycyclic aromatic hydrocarbons via transient directing group strategy has been developed, involving the consecutive arylation, cyclization and aromatization. The efficiency and practicality were demonstrated by wide substrate range, concise synthetic pathway and mild reaction conditions. The subsequent transformations of the benz[a]anthracene core accessed natural bioactive PAH molecules.     

Comparison of T2 and LASER T2dagger image contrast in a rat model of acute cerebral ischemia

Previous studies have shown that T2(dagger)-weighted magnetic resonance images acquired using localization by adiabatic selective refocusing (LASER) can provide early tissue contrast following ischemia, possibly due to alterations in microscopic susceptibility within the tissue. The purpose of this study was to make a direct in vivo comparison of T2-, T2(dagger)- and diffusion-weighted image contrast during acute ischemia. Acute middle cerebral artery (MCA) occlusion was attempted in 14 rats using a modified Tamura approach incorporating electrocoagulation of the left MCA. T2(dagger)-weighted LASER images (Echo Time [TE]=108 ms), T2-weighted Carr-Purcell-Meiboom-Gill (CPMG) images (TE=110 ms) and diffusion-weighted images (b value=105 s/mm(2)) were acquired at 4 T within 1.5 h of ischemia onset. Tissue contrast in the MCA territory was quantified for histologically verified ischemic tissue (n=6) and in sham controls (n=4). T2(dagger)-weighted LASER images demonstrated greater contrast compared to the T2-weighted CPMG images, and more focal contrast compared to the diffusion-weighted images, suggesting different contrast mechanisms were involved.     

An electrochemical modification strategy to fabricate NiFeCuPt polymetallic carbon matrices on nickel foam as stable electrocatalysts for water splitting

Electrochemical modification is a mild and economical way to prepare electrocatalytic materials with abundant active sites and high atom efficiency. In this work, a stable NiFeCuPt carbon matrix deposited on nickel foam (NFFeCuPt) was fabricated with an extremely low Pt load (∼28 μg cm⁻²) using one-step electrochemical co-deposition modification, and it serves as a bifunctional catalyst for overall water splitting and achieves 100 mA cm⁻² current density at a low cell voltage of 1.54 V in acidic solution and 1.63 V in alkaline solution, respectively. In addition, a novel electrolyte was developed to stabilize the catalyst under acidic conditions, which provides inspiration for the development of highly efficient, highly stable, and cost-effective ways to synthesize electrocatalysts.

Multiple metal elements immobilized into a carbon matrix to fabricate an ultra-stable water splitting electrocatalyst by one-step electrochemical modification.     

Electrical Properties of Sol-Gel Processed Hybrid Films

We report on the electrical properties of a hybrid organic/inorganic material synthesized by a sol-gel technique. Spin-coated films with sputtered Nb electrodes in a sandwich-type geometry were studied by a.c. measurements. The aging of the films affected the resistance of the samples. Electrochemical impedance spectroscopy (EIS) measurements were performed in a test chamber at different relative humidity (RH) values to evaluate the aging mechanism.     

金属卟啉-聚乙二醇催化烯烃环氧化反应

研究了聚乙二醇在模拟细胞色素P-450酶、CH_2Cl_2-H_2O两相体系中的相转移催化作用;并和季铵盐类相转移催化作用进行了比较。把PEG-400键联到金属卟啉上,进一步考察了连接大分子后对金属卟啉的催化活性及稳定性的影响;同时比较了键联后的聚乙二醇和自由聚乙二醇所起的相转移催化作用;最后,对反应机理进行了讨论。     

Preparation of Sol-Gel Nano-Composites Containing Copper Oxide and Their Gas Sensing Properties

Sol-gel derived composite materials were prepared with nano-sized copper particles in silica matrix. Nano-sized oxide coatings were grown on the nano-particles of copper by subjecting the composites to a controlled oxidation treatment at different temperatures. The current response of samples with oxide layers of different thickness were studied at fixed temperatures in the range 350–450°C in the presence of different concentrations of CO and NO₂. The nano-composites were sensitive to both the gases. The operating temperature and the oxide thickness were found to have significant effect on the sensing properties.     

Solid-state Fluorescence from Carbon Dots Widely Tunable from Blue to Deep Red through Surface Ligand Modulation

Carbon dots (CDs) find widespread attention due to their remarkable fluorescent and electronic properties. However, aggregation-caused quenching currently limits the application of CDs in colored displays. The construction of CDs with color-tunable solid-state fluorescence (SSF) is rarely reported, since the preparation of SSF CDs is technically challenging. Herein, through surface ligand modulation, SSF CDs with an emission-color span of almost 300 nm (from blue to deep red) were obtained. In-depth structure-property studies reveal that intra- and inter-molecular hydrogen-bonding inside SSF CDs provokes the emission properties in the aggregated state. Photodynamic characterizations demonstrate emission wavelengths can be switched smoothly by deliberately altering conjugation ability between substituent ligands and CDs core. Three-dimensional printing patterning is used to create a range of emissive objects, demonstrating the commercial potential for use in optical lamps.     

Extension of Non-alternant Nanographenes Containing Nitrogen-Doped Stone-Thrower-Wales Defects

Non-alternant topologies have attracted considerable attention due to their unique physiochemical characteristics in recent years. Here, three novel topological nanographenes molecular models of nitrogen-doped Stone–Thrower–Wales (S–T–W) defects were achieved through intramolecular direct arylation. Their chemical structures were unambiguously elucidated by single-crystal analysis. Among them, threefold intramolecular direct arylation compound (C₄₂H₂₁N) is the largest nanographene bearing a N-doped non-alternant topology to date, in which the non-benzenoid rings account for 83 % of the total molecular skeleton. The absorption maxima of this compound was located in the near-infrared region with a long tail up to 900 nm, which was much longer than those reported for similarly sized N-doped nanographene with six-membered rings (C₄₀H₁₅N). In addition, the electronic energy gaps of these series compounds clearly decreased with the introduction of non-alternant topologies (from 2.27 eV to 1.50 eV). It is noteworthy that C₄₂H₂₁N possesses such a low energy gap (E_g^opt=1.40 eV; E_g^cv=1.50 eV), yet is highly stable under ambient conditions. Our work reported herein demonstrates that the non-alternant topology could significantly influence the electronic configurations of nanocarbons, where the introduction of a non-alternanting topology may be an effective way to narrow the energy gap without extending the molecular π-conjugation.